Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/128—Mixtures of organometallic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/46—Titanium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
  • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

• the present invention relates catalyst system for the polymerization of olefins comprising a titanium complex as catalyst component.
• metallocene catalysts have been widely carried out.
• the central metal is Ti, Zr and Hf
• metallocene catalysts a combination of a metallocene compound having a sandwich structure of cyclop entadienyl rings with a Lewis acid compound such as methyl aluminoxane
• ⁇ -olefin such as propylene
• Metallocene compounds having Ti as a central metal have a behavior completely different from those having Zr (zirconocene catalysts) or Hf (hafhocene catalysts). They revealed extremely low polymerization activity as reported in J. Organometallic Chemistry, 479 (1994) 1-29, where the order of polymerization activity depending on central metals results to be Zr>Hf»Ti (page 24, line 13 to 16) or in J. Am. Chem. Soc, 1989, 109, 6544, J. Organometallic Chemistry, 434 (1992) Cl where the polymerization activity of titanocene catalysts has been described to remarkably decline under the polymerization conditions.
• the present invention provides a catalysts system having an enhanced activity comprising the product obtainable by reacting:
• Z and Z' may be identical or different and each represents a ⁇ -bonding ligand or a ⁇ -bonding ligand;
• R" represents a bridging moiety
• Q represents a straight or branched alkyl, aryl, alkenyl, alkylaryl, arylalkyl group or a halogen atom;
• A represents a counteranion;
• (e) k is an integer from 1 to 3;
• ( ) 1 is an integer from 0 to 2;
• (g) m is an integer from 0 to 3; and (C) a Lewis acid compound.
• the catalyst system object of the present invention comprises the product obtainable by reacting:
• Z is an unsubstituted or substituted cyclopentadienyl group, optionally condensed to one or more unsubstituted or substituted, saturated, unsaturated or aromatic rings, containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements;
• Z' is O, S, ⁇ R 1 or PR 1 , R 1 being hydrogen, a linear or branched, saturated or unsaturated C ⁇ C 2 n alkyl, C 3 - C o cycloalkyl, C 6 -C o aryl, C -C o alkylaryl or C 7 -C n arylalkyl, or Z' has the same meaning of Z;
• R" is a divalent radical selected from the group consisting of: linear or branched, saturated or unsaturated -C ⁇ alkylidene, C 3 -C o cycloalkylidene, C 6 -C o arylidene, C 7 -C 2 o alkylarylidene or C -C o arylalkyldene radicals, optionally containing one or more Si, Ge, O, S, P, B or ⁇ atoms;
• Q is selected from the group consisting of, halogen atoms or a linear or branched, saturated or unsaturated C ⁇ -C o alkyl, C 3 -C 2 o cycloalkyl, C 6 -C 2 o aryl, C -C 2 o alkylaryl or C -C 2 o arylalkyl group, optionally containing one or more Si or Ge atoms; k is 2; and m is 0 or 1 ; and
• the oxidizing agents are compounds which can oxidize Ti of low valences Ti [Ti(II), Ti(III)] in a radical coupling manner, preferably the oxidizing agents oxidizes Ti(II) to Ti(IN).
• the oxidizing agents are used in a broader sense than oxidizing agents used in a general mean.
• Some examples of the compounds which oxidatively add to Ti of low valences are known. For example, they are described in "Titanium Complexes in Oxidation States +2 and +3" in Section 4 of Comprehensive Organometallic Chemistry II (Pergamon) Volume 4. However, no example in which these oxidizing agents were used for catalysts system of olefm polymerization has been known.
• Halogenated hydrogen (HC1, HBr, HI, and the like);
• Metallic hydrogenates interstitial compounds each comprising a transition metal and, e.g., PdH x , TiH x and the like.
• Electrophilic reagent for example; Halogens (chlorine, bromine, iodine, and the like); Halogenated alkyl (methyl iodide, and the like); Hypohalogenate salts (NaOCl, KOBr, NaOBr, and the like); Halogenate salts (NaClO 3 , KClO 3 , NaIO 3 , KIO 3 ); Periodate salts and periodic acid (H 5 IO 6 , NaIO , KIO 4 );
• N-halocarboxylate amido N-bromosuccinimide, N-bromoacetamide, N-bromophthalimide, and the like
• R-(X) n -R Sulfides and the like (R-(X) n -R), [wherein X is S or Se atom; R is an alkyl group, an aryl group and the like; n is an integer from 1 to 3; for example, Ph 2 S , trisulfide RSSSR (R -p- tol, t-Pr, t-Bu or CH 2 Ph)]
• Metallic compounds including metallic atoms of high atomic values such as metallic salts, metallic oxides.
• Preferred oxidizing agent are those compounds able to oxidize in a coupling manner Ti(LT) to Ti(IV) for example: halogens (chlorine, bromine, iodine, and the like); halogenated alkyl of formula R 6 T 1 n wherein T 1 a halogen atom, R is a linear or branched, saturated or unsaturated C1-C20 alkyl, C 3 -C 2 o cycloalkyl, -C20 aryl, C 7 -C 2 o alkylaryl or C 7 -C 2 o arylalkyl hydrocarbon in which n hydrogen are substituted with T 1 atoms and n ranges from 1 to 5, preferably n is 1 and T 1 is iodine; examples of these compounds are methyl iodide, methyl bromide, benzil iodide, benzil bromide; transition metal salts of formula T 2 ⁇ wherein T 2 is a metal of group 8-15
• Organic transition metal compound of formula R 6 -T 3 -T 3 -R 6 wherein R 6 , equal to or different from each other, is a linear or branched, saturated or unsaturated -C20 alkyl, C 3 -C 2 o cycloalkyl, C 6 -C 2 o aryl, C -C 2 o alkylaryl or C -C 2 o arylalkyl radical; preferably R 6 is a -Cio alkyl radical; T 3 is tin (Sn) or lead (Pb).
• a titanium complex of the present invention is represented by said general formula (I).
• AUyl, cyclobutadienyl, cyclopentadienyl, arene, cyclooctatetraenyl group, and the like. These may comprise typical elements of 4B, 5B and 6B groups in addition to carbon atoms.
• Example of ⁇ -Bonding ligands are: cyclopentadienyl, mono-, di-, hi- and tetra-methyl cyclopentadienyl; 4-tertbutyl-cyclopentadienyl; 4-adamantyl-cyclopentadienyl; indenyl; mono-, di-, tri- and tetra-methyl indenyl; 4,5,6,7-tetrahydroindenyl; fluorenyl; 5,10-dihydroindeno[l,2- b]indol-10-yl; N-methyl- or N-phenyl-5,10-dihydroindeno [l,2-b]indol-10-yl; 5,6- dihydroindeno[2,l-b]indol-6-yl; N-methyl-or N-phenyl-5,6-dihydroindeno[2,l-b]indol-6-yl; azapen
• 6B group (O, S, Se, Te) alkoxy, aryloxy, alkylthio, arylthio groups preferably the ⁇ -Bonding ligand is a N- methyl, N-ethyl, N-isopropyl, N-butyl, N-phenyl, N- benzyl, N-cyclohexyl or N-cyclododecyl. radical.
• R" is a bridging structure, and the structures represented below can be exemplified. preferably R" is Si(CH 3 ) 2 , SiPh 2 , CH 2 , (CH 2 ) 2 , (CH 2 ) 3 or C(CH 3 ) 2 .
• Q is a methyl, benzyl group or a chlorine atom.
• A is a counter anion, preferably a non- coordinated anion or extremely weakly coordinated anion for titanocene cation.
• the size of A is varied depending on the coordination structure of counter cation of titanocene.
• (e) k is an integer from 1 to 3, preferably k is 2.
• (f) 1 is an integer from 0 to 2.
• the formula (1) is a neutral titanium complex and a catalytic precursor.
• (g) m is an integer from 0 to 3, preferably m is 1.
• Z and Z' are ⁇ -bonding ligands including (substituted) cyclopentadienyl ring
• the structures of Z and Z' are classified as follows depending on the difference of the integer m.
• (substituted) cyclopentadienyl rings are shown as follows; Cp, MeCp, EtCp, ⁇ -PrCp, w-BuCp, l,3-Me 2 Cp, l,3,4-Me 3 C ⁇ , Me 5 Cp, Ind, 2-MeInd, 2-EtInd, 3-Mernd, 3- t-BuInd, 2-t-PrInd, 2,4-Me 2 Ind, 2,4,7-Me 3 Ind, 2-Me-4-z-PrInd, 2-Me-4-PhInd, 2-Me-4-(l- Naph)Ind, 2-Me-Benz[e]Ind, Flu, 2,7-Me 2 Flu, 2,7-t-Bu 2 Flu, wherein the brevity codes mean the following (substituted) cyclopentadienyl groups.
• (substituted) cyclopentadienyl rings containing heteroatoms include 5-methyl- cyclopenteno[b]thiophene, 2,5-dimethyl-l-phenyl cyclopenteno [b] pyrrole, and cyclopenteno[l,2-b.4.3-b 'Jdithiaophene described in J Am. Chem. Soc, 1998, 20, 10786.
• MeCp)(Ind)TiCl 2 Me 2 C(3-MeCp)(2-MeInd)TiCl 2 , Me 2 C(3-MeCp)(3-MeInd)TiCl 2 , Me 2 C(3- MeCp)(3-t-BuInd)TiCl 2 , Me 2 C(3-MeCp)(Flu)TiCl 2 , Me 2 C(3-MeCp)(2,7-Me 2 Flu)TiCl 2 , Me 2 C(3-MeCp)(2,7-t-Bu 2 Flu)TiCl 2 , Me 2 C(3-t-BuCp) 2 TiCl 2 , Me 2 C(3-t-BuCp)(Ind)TiCl 2 , Me 2 C(3-t-BuCp)(2-Memd)TiCl 2 , Me 2 C(3-t-BuCp)(3-Me
• Me 2 C(3-t-BuInd) 2 TiCl 2 Me 2 C(3-t-BuInd)(2,7-t-Bu 2 Flu)TiCl 2> Me 2 Si(Ind)(Flu)TiCl 2; Me 2 Si(3-
• Lewis acid compounds are broadly classified into the following two types.
• organoaluminoxy compounds represented by the general formula (III):
• R 2 ,R 3 and R 4 may be identical to or different from one another, and are hydrogen atoms or hydrocarbon groups with from 1 to 10 carbon atoms, preferably methyl and z-butyl groups; R 5 existing in multiple may be identical to or different from one another, and are hydrocarbon groups with from 1 to 10 carbon atoms, preferably methyl and --butyl groups, and j is an integer from 1 to 100, and preferably the formula is an organoaluminoxy compound consisted of from 3 to 100 of mixtures.
• a method for adding a trialkylaluminum to a suspension of a salt having crystal water (copper sulfate hydrate, aluminum sulfate hydrate, and the like) in a hydrocarbon solvent or a method for applying solid, liquid or gaseous water to a trialkylaluminum can be enumerated.
• n 2 or more and R 5 are identical, one kind of trialkylaluminum is used.
• n 2 or more and R 5 are different, two or more types of trialkylaluminums may be used, or one or more types of trialkylaluminums and one or more types of dialkylaluminum halide may be used.
• trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-z-propylaluminum, tri-n-butylaluminum, tri-z- butylaluminum, tri-5-butylaluminum, tri-t-butylaluminum, tri-(2,4-dimethylbutyl)aluminum, di- «-pentyl-7---butylaluminum, di- «-hexyl-/--butylaluminum, and dicyclohexyl- «- butylaluminum, dialkylaluminum halide such as dimethylaluminum chloride and di- - butylaluminum chloride, as well as dialkylaluminum alkoxides such as dimethylaluminum methoxide, and among them, trialkylaluminum, especially trimethylaluminum and tri-t- butyla
• Another group is the other Lewis acid compounds which form an ionic complex by reacting with a metallocene compound.
• boron compounds are preferred. Specifically, boron compounds having pentafluorophenyl, p-methyl tetrafluorophenyl and j->-trimethylsilyl tetrafluorophenyl groups are preferred.
• organoaluminum compounds can be added if necessary as scavenger.
• organoaluminum compounds are selected from trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-w-propylaluminum, tri-z- propylaluminum, tri- ⁇ -butylaluminum, tri-t-butylaluminum, tri-s-butylaluminum, tri-t- butylaluminum, tri- ⁇ -pentylaluminum, tri-?z-hexylaluminum and tri- ⁇ -octylaluminum, dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride and di-z-butylaluminum chloride, dialkylaluminum alkoxide such as dimethylaluminum methoxide and diethylaluminum ethoxide, dialkylaluminum aryloxide such as diethylaluminum phenoxide, or aluminoxan.
• the above catalytic system can be supported on a fine particle carrier as shown below.
• the average particle diameters of the fine particle carriers used herein are generally from 10 to 300 ⁇ m, preferably from 20 to 200 ⁇ m.
• the fine particles are not especially limited if only they are solid in polymerization solvents, and selected from organic and inorganic substances.
• inorganic substances inorganic oxides, inorganic chlorides, inorganic carbonates, inorganic sulfates, and inorganic hydroxides are preferable, and as organic substances, organic polymers are preferred.
• oxides such as silica and alumina, chlorides such as magnesium chloride, carbonates such as magnesium carbonate and calcium carbonate, sulfates such as magnesium sulfate and calcium sulfate, as well as hydroxides such as magnesium hydroxide and calcium hydroxide
• organic carriers fine particles of organic polymers such as polyethylene, polypropylene and polystyrene can be exemplified.
• the preferred are inorganic oxides, and especially silica, alumina and combined oxides thereof are preferable.
• porous fine particle carriers are especially preferred since few polymers adhere to inside walls of reaction vessels and thus resultant bulk density of the polymers becomes high.
• specific surface areas are preferably in the range of from 10 to 1000 m 2 /g, more preferably in the range of from 100 to 800 m /g, and especially the range of from 200 to 600 m /g is preferred. And for the pore volumes, the range of from 0.3 to 3 mL/g is preferable, and the range of from 1.0 to 2.0 mL/g is most preferable.
• the volumes of absorbed water and surface hydroxyl groups become different depending on their treatment conditions.
• the preferred water content is 5 wt% or less, and the preferred volume of surface hydroxyl groups is 1/nm 2 or more per surface area.
• the control of volumes of water contents and surface hydroxyl groups can be carried out by calcination temperature or treatment with organoaluminum compounds or organic boron compounds.
• the contact timing of the oxidizing agents with the titanium complex and the Lewis acid compounds at the polymerization reaction can be optionally selected.
• the method where after the titanium complex is first contacted with the Lewis acid compound (pre-contact) followed by contact with the oxidizing agent, this catalytic system is added to olefins thereby initiating the polymerization reaction is included.
• the method where the titanium complex is first contacted with the oxidizing agent followed by contact with the Lewis acid compound for polymerization may be used.
• a method in which the oxidizing agent and the olefm monomer are charged in a reaction vessel, and a catalyst comprising the titanium complex having the Lewis acid compound contacted there with is introduced thereinto, thereby initiating the polymerization.
• the concentrations of the catalyst components are not especially limited, but the molar ratio of [oxidizing agent]/[titanium complex] for the concentration of the oxidizing agent is from 10 " to 10 , and especially the range of from 10 "1 to 10 2 is preferred.
• concentration of titanium complex the range of from 10 "3 to 10 "10 mol/L is preferable.
• concentration of (C-l) the organoaluminoxy compound the molar ratio of [aluminum atoms in organoaluminoxy compound]/[titanium complex] is from 10 to 10,000, especially the range of from 100 to
• [boron compound]/[titanium complex] is from 0.1 to 100, and the range of from 0.2 to 10 is most preferable.
• the objective of the present invention can be achieved by bubbling the oxidizing agent into the solution of titanium complex (and the contact solution of Lewis acid compound) at a flow rate of from 1 to 10 8 mL/min for one or more seconds.
• Z and Z' may be identical or different and each represents a ⁇ -bonding ligand or a ⁇ -bonding ligand;
• R" represents a bridging moiety
• Q represents a straight or branched alkyl, aryl, alkenyl, alkylaryl, arylalkyl group or a halogen atom
• (e) k is an integer from 1 to 3;
• (f) 1 is an integer from 0 to 2;
• (g) m is an integer from 0 to 3;
• (C) a Lewis acid compound; characterized in that hydrogen is bubbled in a solution of the titanium complex or in a solution of the reaction product of the titanium complex and the Lewis acid prior of the introduction of the catalyst system in the polymerization reactor.
• polymerization of olefins can be carried out by any polymerization methods known in the art such as solution polymerization, slurry polymerization, gas phase polymerization and bulk polymerization.
• the condition of polymerization is not especially limited, but the temperature of polymerization at from -100 to 100°C is preferable.
• the control of molecular weights at polymerization can be performed by the methods known in the art, e.g., selection of the temperature and introduction of hydrogen.
• a further object of the present invention is a process for polymerizing one or more alpha olefins comprising the step of contacting under polymerization condition one or more alpha olefins in the presence of the catalyst system object of the present invention.
• the olefins used for polymerization in the present invention can include ethylene, propylene,
• olefins can be polymerized alone or copolymerized with two or more types.
• the polymerization was carried out under the same condition as that in Example 1 except not bubbling hydrogen for 2 min.
• the polymerization was carried out under the same condition as that in Example 1 except introducing hydrogen at a hydrogen propylene concentration ratio of 36 mol ppm into polymerization.
• the polymerization was carried out under the same condition as that in Example 2 except not bubbling hydrogen for 2 min.
• the polymerization was carried out under the same condition as that in Example 1 except introducing hydrogen at a hydrogen/propylene concentration ratio of 145 mol ppm into polymerization system.
• the polymerization was carried out under the same condition as that in Example 1 except introducing hydrogen at a hydrogen/propylene concentration ratio of 36 mol ppm into polymerization using t/zreo-z ' -Pr(3-t-BuCp)(3-t-BuInd)TiCl 2 (synthesized according to
• the polymerization was carried out under the same condition as that in Example 4 except not bubbling hydrogen for 2 min.
• Example 5 The polymerization was carried out under the same condition as that in Example 5 except adding 6.6 mg (20 ⁇ mol) of hexamethyl ditin as an oxidizing agent in Example 5.
• Example 5 The polymerization was carried out under the same condition as that in Example 5 except adding 0.12 mL (1.0 mmol) of methyl iodine as an oxidizing agent in Example 5.
• Example 5 The polymerization was carried out under the same condition as that in Example 5 except adding 5.1 mg (20 ⁇ mol) of iodine as an oxidizing agent in Example 5.

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